Fine zeolite particle

ABSTRACT

A fine A-type zeolite particle having an average primary particle size of 0.1 μm or less and a variation coefficient of 90% or less, wherein a ratio of a peak area above a background level to all peak are in the range of 2θ=20° to 40° in a powder X-ray diffraction spectrum of said fine A-type zeolite particle is 30% or more; a process for preparing the fine A-type zeolite particle, comprising reacting a silica source with an aluminum source in the presence of an organic compound having an oxygen-containing functional group and a molecular weight of 100 or more; and a detergent composition comprising a surfactant and the fine A-type zeolite particle. The fine zeolite particle is suitably used for detergent builders, water treatment agents, fillers for paper, resin fillers, oxygen-nitrogen separating agents, adsorbents, catalyst carriers, soil improvers for gardening, polishing agents, and the like.

This application is the national phase under 35 U.S.C. §371 of PCTInternational Application No. PCT/JP01/11326 which has an Internationalfiling date of Dec. 25, 2001, which designated the United States ofAmerica.

TECHNICAL FIELD

The present invention relates to a fine zeolite particle, a process forpreparing the same, and a detergent composition comprising the finezeolite particle.

BACKGROUND ART

Zeolites are crystalline aluminosilicates, which can be classified intovarious crystal structures such as A-type, X-type and Y-type by thearrangements of SiO₄ tetrahedrons and AlO₄ tetrahedrons. The zeoliteshave an even pore size depending upon the crystal structures, therebyexhibiting a molecular sieve function. For the reason, the zeolites havebeen used for adsorbents, catalysts (carriers) and the like. Inaddition, since the zeolites have cationic exchange abilities, they havebeen utilized as detergent builders, agents for waste water treatment,and the like.

The functions of the zeolites greatly depend on the crystal structureand the composition of the zeolite. For instance, the smaller the Si/Almolar ratio of the zeolite, the larger the cationic exchange capacity,and theoretically an A-type zeolite of which Si/Al is 1 is mostexcellent. Therefore, the A-type zeolites having a high cationicexchange theoretical capacity have been mainly used as detergentbuilders.

Further, as detergent builders, there are especially needed zeolitesexcellent in not only the calcium ion exchange capacity but also thecalcium ion exchange rate. This is because when calcium ions in waterespecially at an initial stage of washing can be captured in largeamounts, the detergency performance is improved. Since the calcium ionexchange rate of the zeolite is determined by a collision probability ofthe calcium exchange site of the zeolite with the calcium ions in water,the smaller the primary particle size of the zeolite, the higher thecalcium ion exchange rate of the zeolite.

In view of above, various proposals for preparing A-type zeolites havinga very small primary particle size have been so far made. For instance,Japanese Patent Laid-Open No. Sho 54-81200 discloses a process forpreparing a fine A-type zeolite particle comprising carrying out thereaction in the co-existence of an organic acid such as formic acid oracetic acid in a reaction mixture. However, in this process, theresulting zeolite particle only has a primary particle size of at least0.5 μm. On the other hand, Japanese Patent Laid-Open No. Hei 1-153514discloses a process for preparing a fine A-type zeolite particle havinga maximal particle size of 0.4 μm or less, comprising forming a zeolitenucleus at a temperature of 40° C. or less. However, even in thisprocess, the formed A-type zeolite particle has a primary particle sizeof at least 0.2 μm.

Meanwhile, a largest defect of the zeolite builder is in that zeolitemakes water turbid due to its water insolubility. In view of thisproblem, there has been proposed to reduce turbidity of the zeolite bymaking an aggregate particle size of the zeolite small to a size ofequal to or less than a wavelength of visible light (0.4 μm) [Okumura,Nendo Kagaku 27, 21 (1987)]. In other words, the turbidity of thewashing water is reduced with making the aggregate particle sizesmaller, and when the aggregate particle size is 0.4 μm or less, thewashing water (zeolite concentration: 0.013% by weight) becomes almosttransparent. However, when the A-type zeolite of which aggregateparticle size is made very fine to the order of submicron size is madeinto a powdery state, the powder then re-aggregates to undesirably forma large aggregate. Also, it is very difficult to carry out solid-liquidseparation for the zeolite by means of filtration or concentration.Therefore, the zeolite has been actually fed to the detergent rawmaterial in a slurry state. At this time, the existence of Al ions inthe slurry (unreacted compounds of the zeolite raw materials orzeolite-eluted products) could be a factor of lowering the detergencyperformance. Therefore, the Al ion concentration in the slurry must becontrolled to a low level.

Generally, the aggregate particle size of A-type zeolite is made smallerby means of vigorous stirring, pulverization or the like. For instance,as disclosed in Japanese Patent Laid-Open No. Hei 9-67117, an aggregateparticle size and a primary particle size are made smaller to the orderof submicron size by mechanical pulverization. However, when an A-typezeolite having a large primary particle size is subjected topulverization treatment, the cationic exchange abilities, i.e. thecationic exchange capacity and the cationic exchange rate, areundesirably lowered due to the crystallinity degradation caused by thedisintegration of primary crystals of the A-type zeolite and thedeterioration of the primary particle size distribution. In addition, ina water-based liquid of the zeolite after the pulverization treatment,ions of zeolite-constituting elements, i.e. Al, Si, and Na, especiallyAl, tend to be easily eluted in water, by the mechanochemical reactionof the zeolite particle surface. Therefore, when the zeolite is used fora detergent composition, there also arises a problem that the detergencyperformance of the composition is lowered.

In order to suppress the generation of the problems due to the processof making the aggregate particle size of the zeolite smaller, thedisintegration of the zeolite primary crystals by the process of makingthe size fine must be avoided. In order to avoid the disintegration, itis desired that the primary particle size of A-type zeolite beforepulverization is equal to or less than the aggregate particle size ofthe zeolite after pulverization. Concretely, when the average aggregateparticle size is made smaller to a size of 0.4 μm or less, the averageprimary particle size is generally 0.1 μm or less. On the basis of thisfact, it is considered to be desirable that the average primary particlesize of A-type zeolite before pulverization is 0.1 μm or less in orderto suppress the generation of the problems mentioned above and to makethe zeolite particle smaller by pulverizing the particle until theparticle has an average aggregate particle size (0.4 μm or less) whichgives almost transparent washing water (zeolite concentration: 0.013% byweight). In addition, as long as a zeolite has the average primaryparticle size mentioned above, a desired average aggregate particle sizecould be obtained without subjecting the zeolite to pulverizationtreatment. However, as mentioned above, there are no examples of aprocess for preparing a fine A-type zeolite particle having an averageprimary particle size of 0.1 μm or less without carrying outpulverization treatment or the like after the reaction for preparing thezeolite.

An object of the present invention is to provide a fine A-type zeoliteparticle having an average primary particle size of 0.1 μm or less and avariation coefficient of 90% or less, and excellent in the cationicexchange capacity, and giving small amounts of Al eluted in water andlittle water turbidity in a water-based liquid, a process for preparingthe fine A-type zeolite particle, and a detergent composition comprisingthe fine A-type zeolite particle (hereinafter simply referred to as“fine zeolite particle or fine zeolite particles”), which is veryexcellent in the detergency and the rinsing performance.

These and other objects of the present invention will be apparent fromthe following description.

DISCLOSURE OF INVENTION

According to the present invention, there is provided:

(1) A fine A-type zeolite particle having an average primary particlesize of 0.1 μm or less and a variation coefficient of 90% or less,wherein a ratio of a peak area above a background level to all peak areain the range of 2θ=20° to 40° in a powder X-ray diffraction spectrum ofsaid fine A-type zeolite particle is 30% or more;

(2) a process for preparing the fine A-type zeolite particle of item (1)above, comprising reacting a silica source with an aluminum source inthe presence of an organic compound having an oxygen-containingfunctional group and a molecular weight of 100 or more; and

(3) a detergent composition comprising a surfactant and the fine A-typezeolite particle of item (1) above.

BEST MODE FOR CARRYING OUT THE INVENTION

The fine zeolite particle of the present invention can be prepared byreacting a silica source with an aluminum source in the presence of anorganic compound having an oxygen-containing functional group and amolecular weight of 100 or more. By carrying out the reaction forpreparing the zeolite as described above, the crystal growth of thezeolite can be suppressed, whereby a fine A-type zeolite particle havingan average primary particle size of 0.1 μm or less can be formed. In thefine zeolite particle obtained as described above, even if the particlewere desirably further made smaller by mechanical pulverization or thelike until the particle has an average aggregate particle size of 0.4 μmor less which gives substantially transparent washing water (zeoliteconcentration: 0.013% by weight), the crystallinity degradation, thedeterioration of the average primary particle size distribution and theelution of Al (Al ion) can be suppressed.

Specifically, the fine zeolite particle of the present invention is anA-type zeolite having an average primary particle size of 0.1 μm or lessand a variation coefficient of 90% or less. The zeolite is excellent inthe cationic excellent abilities, and gives substantially no elution ofAl ions into water from the zeolite in a water-based liquid containingthe zeolite and little water turbidity of the liquid.

The term “water-based liquid” as referred to herein is a liquidcomprising certain components and water as a medium including an aqueoussolution, a suspension, a dispersion or the like.

The fine zeolite particle of the present invention has an averageprimary particle size of 0.1 μm or less, preferably 0.08 μm or less,more preferably 0.05 μm or less. As mentioned above, when the averageaggregate particle size is made smaller by pulverization from theviewpoint of improving the turbidity of washing water, there arise someproblems such as crystallinity degradation of the zeolite. The extent ofgeneration of the problems depends on the average primary particle sizeof zeolite before pulverization: The larger the average primary particlesize, the more serious the problem. Generally, in a A-type zeolitehaving an average primary particle size larger than 0.1 μm, the primarycrystal itself is disintegrated by pulverization, so that the ions ofconstituent elements are eluted from the zeolite in large amounts andthe crystallinity degradation progresses drastically as mentioned above.Since the fine zeolite particle of the present invention has an averageprimary particle size within the above-mentioned range, the generationof the problems caused by pulverization would be substantiallycompletely suppressed. The average primary particle size can bedetermined by the method described in Examples set forth below.

The particle size distribution of the zeolite having the average primaryparticle size in the range mentioned above can be evaluated by variationcoefficient The variation coefficient can be calculated according to themethod described in Examples set forth below. The particle sizedistribution of the fine zeolite particle of the present invention ishighly uniform satisfying the variation coefficient of theabove-mentioned average primary particle size of 90% or less, preferably70% or less, more preferably 50% or less, still more preferably 35% orless. In other words, the fine zeolite particle of the present inventionis composed of a zeolite having a desired average primary particle sizeof 0.1 μm or less and a uniform particle size distribution, whichcontributes to the exhibition of excellent cationic exchange abilities.In an A-type zeolite having a large average primary particle size of 1μm or more, the state of disintegration of the primary crystals causedby pulverization can be captured by scanning electron microscope, andthe variation coefficient of the average primary particle size becomesgenerally large by the pulverization. On the other hand, in the finezeolite particle of the present invention, the disintegration of theprimary crystals caused by pulverization is substantially completelysuppressed, and an aggregate of the primary particles is merelydisaggregated during the pulverization. Therefore, the changes in thevariation coefficient caused by pulverization do not substantially takeplace.

The fine zeolite particle of the present invention is an A-type zeolite,which can show substantially the same powder X-ray diffraction patternas that of a known A-type zeolite (Joint Committee on Powder DiffractionStandards No. 38-241). Here, as long as the powder X-ray diffractionpattern of the fine zeolite particle is substantially the same as thatof a known one, the pattern may contain peaks ascribed to othercrystalline substances and halo peaks belonging to amorphous substances.In addition, a ratio (powder X-ray diffraction intensity ratio) of apowder X-ray diffraction peak intensity I₄₁₀ of the fine zeoliteparticle of the present invention to an I₄₁₀ of d=0.3 nm belonging to aplane (410) of a commercially available A-type zeolite (for instance,“TOYOBUILDER” manufactured by Tosoh Corporation) having an averageprimary particle size of 1 μm or more is preferably 10% or more, morepreferably 20% or more, from the viewpoint of improving the cationicexchange abilities.

In addition, the crystallinity of the fine zeolite particle of thepresent invention can be evaluated by a ratio (A_(r)) of a peak areaabove the background level in all peak area in the range of 2θ=20° to40° in the powder X-ray diffraction spectrum. The A_(r) can beconcretely calculated by the method described in Examples set forthbelow. The fine zeolite particle of the present invention has A_(r) of30% or more, preferably 33% or more, within which range the proportionof amorphous portions in the primary crystal structure is small,excellent cationic exchange abilities can be exhibited, and the loweringof the detergency performance due to elution of Al ions can besuppressed.

On the other hand, since the A_(r) shows the crystallinity of thezeolite, an extent of the crystallinity degradation caused bypulverization can be evaluated as a crystallinity degradation ratio onthe basis of A_(r) obtained before and after the pulverization. Thecrystallinity degradation ratio can be calculated by the methoddescribed in Examples set forth below. In the fine zeolite particle ofthe present invention, the crystallinity degradation ratio is preferably50% or less, more preferably 40% or less, still more preferably 35% orless, from the viewpoints of keeping primary crystallinity, therebysuppressing the lowering of cationic exchange abilities and the elutionof Al ions.

The fine zeolite particle of the present invention has an averageaggregate particle size of preferably 0.4 μm or less, more preferably0.3 μm or less. The average aggregate particle size can be determined bythe method described in Examples set forth below. The degree ofturbidity by the fine zeolite particle of the present invention can bealso determined as turbidity by the method described in Examples setforth below. When the average aggregate particle size is within therange mentioned above, the turbidity can be preferably 30% or less, morepreferably 20% or less. When the average aggregate particle size and theturbidity are within the above ranges, in the case, for instance, wherethe zeolite is added to a detergent composition such as a laundrypowdery detergent and a laundry liquid detergent, it is preferablebecause the water turbidity of washing water and initial rinsing wateris remarkably improved so that the water becomes substantiallytransparent, and a problem that the zeolite remains on a fiber surfacedoes not also take place.

When the fine zeolite particle does not have an average aggregateparticle size of 0.4 μm or less as a primary product obtained by theprocess for preparing the fine zeolite particle of the present inventiondescribed below, the fine zeolite particle may be further subjected topulverization as described below as desired. As described above, sincethe fine zeolite particle of the present invention has an averageprimary particle size of 0.1 μm or less, the lowering of primarycrystallinity is small even if subjected to appropriate pulverization togive an average aggregate particle size of 0.4 μm or less. Therefore,substantially no problems on the lowering of cationic exchange abilitiesand on the elution of Al in large amounts take place. In the presentinvention, it is preferable that the fine zeolite particle obtained as aprimary product is appropriately pulverized, from the viewpoint offurther improving the transparency of washing water, when the finezeolite particle of the present invention is used as a detergentbuilder.

In addition, when the water-based liquid of the fine zeolite particle ofthe present invention is prepared, the ratio of the amount of Al elutedin water is preferably less than 4% by weight, more preferably 3.5% byweight or less, still more preferably 3.2% by weight or less, of theentire amount of Al contained in the fine zeolite particle. It ispreferable that the proportion of the amount of Al eluted is within therange mentioned above, because in the case where the fine zeoliteparticle is added to, for instance, a detergent composition, thelowering of qualities (detergency performance, storage stability and thelike) of the detergent composition can be suppressed. In addition, thelowering of primary crystallinity and the amount of Al eluted are smalleven if subjected to appropriate pulverization to give an averageaggregate particle size within the desired range. The proportion of theamount of Al eluted in water can be determined by the method describedin Examples set forth below.

Also, the fine zeolite particle of the present invention is excellent inthe cationic exchange abilities. Here, the term “cationic exchangeabilities” refer to both the cationic exchange rate and the cationicexchange capacity. More concretely, the term “cationic exchange rate”refers to an amount of Ca which is ion-exchanged per one gram of azeolite in one minute, and the term “cationic exchange capacity” refersto an amount of Ca which is ion-exchanged per one gram of a zeolite inten minutes. The cationic exchange rate and the cationic exchangecapacity can be determined by the methods described in Examples setforth below.

The above-mentioned cationic exchange rate (CER) is preferably 180 mgCaCO₃/g or more, more preferably 200 mg CaCO₃/g or more, still morepreferably 220 mg CaCO₃/g or more. On the other hand, theabove-mentioned cationic exchange capacity (CEC) is preferably 200 mgCaCO₃/g or more, more preferably 210 mg CaCO₃/g or more, still morepreferably 220 mg CaCO₃/g or more. It is preferable that the cationicexchange abilities of the fine zeolite particle of the present inventionare within the above ranges, because in a case where the zeolite is usedfor a detergent composition, the detergency performance of thecomposition is remarkably improved. In addition, there are littlecrystallinity degradation and deterioration of particle sizedistribution even if subjected to appropriate pulverization to give anaverage aggregate particle size within the desired range. Therefore,there are substantially no changes in the cationic exchange abilities.

The fine zeolite particle of the present invention has a composition, inthe anhydride form, represented by the general formula xM₂O.ySiO₂.Al₂O₃.zMeO, wherein M is an alkali metal atom, Me is an alkalineearth atom. In the formula, it is preferable that x is from 0.2 to 4, yis from 0.5 to 6, and z is from 0 to 0.2, and it is more preferable thatx is from 0.8 to 2, y is from 1 to 3, and z is from 0.001 to 0.1. Thoseelements other than the elements given in the above compositionalformula can be contained in the composition within the range so as notto lower the cationic exchange abilities. The above-mentioned alkalimetal atom refers to those elements belonging to Group IA of thePeriodic Table, and is not particularly limited. Among the alkali metalatoms, sodium is preferable. The fine zeolite particle of the presentinvention can contain two or more alkali metal atoms. In addition, theabove-mentioned alkaline earth metal atom refers to those elementsbelonging to Group IIA of the Periodic Table, and is not particularlylimited. Among the alkaline earth metal atoms, calcium and magnesium arepreferable. The fine zeolite particle of the present invention cancontain two or more alkaline earth metal atoms.

Next, the process for preparing a fine zeolite particle of the presentinvention will be described. One of the greatest features of the processresides in that a silica source is reacted with an aluminum source inthe presence of an organic compound having an oxygen-containingfunctional group and a molecular weight of 100 or more (hereinafterreferred to as “crystallization inhibitor”). Since the reaction iscarried out in the presence of the crystallization inhibitor, theflowability of the reaction mixture (slurry) comprising a silica sourceand an aluminum source is increased, thereby improving the reactionefficiency. At the same time, the crystal growth of the zeolite issuppressed, so that the zeolite particle having small average primaryparticle size and even particle size distribution can be formed.

The mechanism for suppression of the zeolite crystal growth by thecoexistence of the above-mentioned crystallization inhibitor ispresumably as follows: Silanol (Si—OH) group or the like on the surfaceof a zeolite nucleus interacts with oxygen atom of the functional groupvia a hydrogen bonding-like interaction, so that the zeolite nucleussurface is stabilized, thereby suppressing the crystal growth (Ostwaldgrowth). Also, the zeolite nucleus themselves are sterically repulseddue to the steric hindrance of the crystallization inhibitors adsorbedto (interacting with) the zeolite nucleus, whereby the crystal growth bycollision of the zeolite nuclei themselves is inhibited. As a result, afine zeolite particle having a small average primary particle size isformed.

The silica source and the aluminum source which are used in the processfor preparing a fine zeolite particle of the present invention are notparticularly limited. For instance, as the silica source, a commerciallyavailable water glass can be used, and silica rock, silica sand,cristobalite, kaolin, cullets, and the like can be also used. Further,they may be properly diluted with water or an aqueous alkali metalhydroxide upon use. In addition, as the aluminum source,aluminum-containing compounds such as aluminum hydroxide, aluminumsulfate, and aluminum chloride can be used, and powder or a water-basedliquid of an alkali metal aluminate, especially sodium aluminate, ispreferably used. These compounds may be commercially available products.As the water-based liquid of sodium aluminate, those obtained bydissolving aluminum hydroxide and an alkali metal hydroxide in waterwith heating can be used.

The crystallization inhibitor has a molecular weight of 100 or more,preferably 200 or more, more preferably 400 or more. When the molecularweight of the crystallization inhibitor is less than 100, there islittle steric hindrance of the crystallization inhibitor adsorbed to(interacting with) the zeolite nucleus surface, so that the progress ofthe crystal growth by collision of the zeolite nuclei themselves cannotbe effectively suppressed, whereby a desired crystallization inhibitingeffect cannot be obtained. In addition, the molecular weight of thecrystallization inhibitor is preferably 60000 or less, more preferably30000 or less, still more preferably 10000 or less, within which rangethe crystallization inhibitor is sufficiently dissolved in the reactionmixture comprising a silica source and an aluminum source, so that theamount of the crystallization inhibitor adsorbed to the zeolite nucleus(amount of the crystallization inhibitor interacting with the zeolitenucleus) is increased, whereby a crystallization inhibiting effect issufficiently exhibited. Especially, the crystallization inhibitor has amolecular weight of preferably from 100 to 60000, more preferably from200 to 30000, still more preferably from 400 to 10000. In the presentinvention, when the crystallization inhibitor has one or more hydroxylgroups or one or more carboxyl groups at one end or both ends, themolecular weight of the crystallization inhibitor can be determined byquantitative analysis of functional groups, for instance, the analysisof hydroxyl value or acid value. In addition, for instance, when themolecular weight is 1000 or more, the molecular weight is aweight-average molecular weight, which can be determined by GPC (gelpermeation chromatography) in accordance with a known method.

The functional group of the crystallization inhibitor is notparticularly limited, as long as it contains oxygen atom. The preferableoxygen-containing functional group includes, for instance, OR group,COOR group, SO₃R group, PO₄R group, CO group, CONH group, and the like,among which OR group and/or COOR group is more preferable. R is at leastone member selected from a saturated or unsaturated organic group having1 to 22 carbon atoms, hydrogen atom and an alkali metal atom. Thesaturated or unsaturated organic group having 1 to 22 carbon atomsincludes, for instance, ethylene group, vinyl group, phenyl group, hexylgroup, dodecyl group, and the like. The alkali metal atom includes, forinstance, sodium, potassium, and the like. These functional groups mayconstruct a main chain, or they may construct a side chain. The numberof functional groups per one molecule of the crystallization inhibitoris not particularly limited. The number of functional groups per onemolecule is preferably 2 or more, more preferably 3 or more, still morepreferably 4 or more. It is preferable that the number of functionalgroups per one molecule is within the above range, from the viewpoint ofgiving a sufficient number of interaction site of the zeolite nucleusand the crystallization inhibitor, thereby giving an excellentcrystallization inhibiting effect of the zeolite. In addition, thenumber of functional groups per one molecule is preferably 1000 or less,more preferably 500 or less, still more preferably 200 or less. It ispreferable that the number of functional groups per one molecule iswithin the above range, from the viewpoints of giving appropriatemolecular weight of the crystallization inhibitor for sufficientlydissolving the compound in a reaction mixture, whereby exhibiting anexcellent crystallization inhibiting effect.

Concrete examples of the crystallization inhibitor include nonionicsurfactants such as polyoxyethylene lauryl ether; and water-solublepolymers such as polyethylene glycol, polyvinyl alcohols, acrylate-basedpolymers, carboxymethyl cellulose and hexametaphosphate; and the like,without being limited thereto. These compounds can be used as a mixtureof two or more kinds.

The feeding composition for preparing the fine zeolite particle of thepresent invention, as expressed by an SiO₂/Al₂O₃ molar ratio, ispreferably 0.5 or more, more preferably 1 or more, still more preferably1.5 or more. It is preferable that the SiO₂/Al₂O₃ molar ratio is withinthe above range, from the viewpoints of stabilizing the crystalstructure of the zeolite, thereby suppressing the lowering ofcrystallinity, and accelerating the progress of crystallization. Inaddition, the SiO₂/Al₂O₃ molar ratio is preferably 4 or less, morepreferably 3 or less, still more preferably 2.5 or less. It ispreferable that the SiO₂/Al₂O₃ molar ratio is within the above range,from the viewpoints of favorably progressing the reaction, therebygiving sufficient cationic exchange abilities.

Also, the feeding composition of the compound containing an alkalimetal, as expressed by an M₂O/Al₂O₃ molar ratio, the alkali metal (M)being shown as an oxide, is preferably 0.08 or more, more preferably 0.8or more, still more preferably 1.4 or more. It is preferable that theM₂O/Al₂O₃ molar ratio is within the above range, from the viewpoint ofaccelerating the progress of crystallization. In addition, the M₂O/Al₂O₃molar ratio is preferably 20 or less, more preferably 5 or less, stillmore preferably 3 or less. It is preferable that the M₂O/Al₂O₃ molarratio is within the above range, from the viewpoint of favorableproductivity.

Further, the feeding composition of the compound containing an alkalimetal and water in the reaction system, as expressed by an M₂O/H₂O molarratio, is preferably 0.02 or more, more preferably 0.05 or more, stillmore preferably 0.07 or more. It is preferable that the M₂O/H₂O molarratio is within the above range, from the viewpoint of giving anappropriate crystallization rate, thereby favorably progressing theformation of the fine zeolite particle with small average primaryparticle size. In addition, the M₂O/H₂O molar ratio is preferably 0.2 orless, more preferably 0.15 or less, still more preferably 0.1 or less.It is preferable that the M₂O/H₂O molar ratio is within the above range,from the viewpoint of properly progressing the reaction, thereby givingsufficient cationic exchange abilities.

Furthermore, the feeding composition of the compound containing analkaline earth metal, as expressed by an MeO/Al₂O₃ molar ratio, thealkaline earth metal (Me) being shown as an oxide, is preferably 0 to0.1. The MeO/Al₂O₃ molar ratio is more preferably 0.005 or more, stillmore preferably 0.01 or more, from the viewpoints of accelerating makingthe average primary particle size fine and improving thermal stability.In addition, the MeO/Al₂O₃ molar ratio is preferably 0.1 or less, morepreferably 0.08 or less, still more preferably 0.05 or less, from theviewpoint of improving the ion exchange abilities.

Moreover, the feeding composition of the aluminum in the reactionsystem, as expressed by an Al₂O₃/H₂O molar ratio, is preferably 0.01 ormore, more preferably 0.02 or more, still more preferably 0.03 or more.It is preferable that the Al₂O₃/H₂O molar ratio is within the aboverange, from the viewpoints of excellent productivity and acceleration ofmaking the average primary particle size fine. In addition, theAl₂O₃/H₂O molar ratio is preferably 0.25 or less, more preferably 0.2 orless, still more preferably 0.1 or less. It is preferable that theAl₂O₃/H₂O molar ratio is within the above range, from the viewpoint ofgiving an excellent flowability to the slurry, thereby efficientlyprogressing the reaction.

When the solid content is defined as a total weight of each inorganicelement contained in the raw materials used constituting the finezeolite particle of the present invention calculated as an oxide, andthe concentration of the solid content during the reaction is defined asthe concentration of the solid content in the entire water-containingslurry, the concentration of the solid content is preferably 10% byweight or more, more preferably 20% by weight or more, still morepreferably 30% by weight or more, from the viewpoint of productivity Inaddition, the concentration of the solid content is preferably 70% byweight or less, more preferably 60% by weight or less, still morepreferably 50% by weight or less, from the viewpoint of the flowabilityof the slurry.

On the other hand, the feeding amount of the above-mentionedcrystallization inhibitor is preferably 1% by weight or more, morepreferably 5% by weight or more, still more preferably 10% by weight ormore, in the reaction mixture comprising a silica source and an aluminumsource, from the viewpoint of exhibiting a crystallization inhibitingeffect. In addition, the feeding amount of the above-mentionedcrystallization inhibitor is preferably 80% by weight or less, morepreferably 60% by weight or less, still more preferably 50% by weight orless, from the viewpoint of productivity.

The fine zeolite particle of the present invention is, for instance,prepared by feeding a silica source, an aluminum source and acrystallization inhibitor each in a separate vessel, and properly mixingthese components in accordance with a known method to react thecomponents. During the reaction, other components may be added withinthe range so as not to hinder the preparation of the fine zeoliteparticle of the present invention. Such other components include, forinstance, calcium chloride, magnesium chloride and the like. It ispreferable that each of the silica source, the aluminum source and thecrystallization inhibitor is fed to the reaction in the form ofwater-based liquid, from the viewpoint of homogeneously and efficientlycarrying out the reaction.

The mixing order of the silica source, the aluminum source and thecrystallization inhibitor is not particularly limited. A liquid mixtureof the aluminum source and the crystallization inhibitor may be mixedwith the silica source, or a liquid mixture of the silica source and thecrystallization inhibitor may be mixed with the aluminum source.Alternatively, the silica source and the aluminum source may besimultaneously fed to the crystallization inhibitor, and mixed; or thecrystallization inhibitor may be previously mixed with the silica sourceand/or the aluminum source, and the silica source is then mixed with thealuminum source.

In addition, the mixing method is not particularly limited. Forinstance, the silica source, the aluminum source and the crystallizationinhibitor may be subjected to line-mixing, with circulating the silicasource, the aluminum source and the crystallization inhibitor togetherin a specified circulation line. Alternatively, the silica source, thealuminum source and the crystallization inhibitor may be mixed in areaction vessel (batch-type mixing). The reaction time is notparticularly limited because it depends upon the reaction temperature.The reaction time is preferably 30 seconds or more, more preferably 1minute or more, still more preferably 5 minutes or more, from thetermination of adding all the feeding components, from the viewpoint ofthe homogeneity of reaction. Also, the reaction time is preferably 120minutes or less, more preferably 60 minutes or less, still morepreferably 30 minutes or less, from the viewpoint of productivity.

The reaction temperature is preferably 10° C. or more, more preferably20° C. or more, still more preferably 40° C. or more. It is preferablethat the reaction temperature is within the range specified above, fromthe viewpoints of giving excellent flowability of the reaction mixtureand carrying out homogeneous reaction. Also, the reaction temperature ispreferably 100° C. or less, more preferably 90° C. or less, still morepreferably 80° C. or less. It is preferable that the reactiontemperature is within the range specified above, from the viewpoints ofproper energy load and an economical advantage on an industrial scale.

The crystallization can be carried out by aging the reaction mixtureafter the reaction at a temperature equal to or higher than the reactiontemperature under stirring. The aging temperature is not particularlylimited. The aging temperature is preferably 50° C. or more, morepreferably 70° C. or more, still more preferably 80° C. or more, fromthe viewpoint of the crystallization rate. In addition, the agingtemperature is preferably 120° C. or less, more preferably 100° C. orless, still more preferably 90° C. or less, from the viewpoints ofenergy load and pressure resistance of the reaction vessel. Although theaging time depends upon the aging temperature, the aging time ispreferably 1 minute or more, more preferably 10 minutes or more, stillmore preferably 30 minutes or more, from the viewpoint of sufficientlycarrying out the crystallization. In addition, the aging time ispreferably 300 minutes or less, more preferably 180 minutes or less,still more preferably 120 minutes or less, from the viewpoints of thelowering of cationic exchange abilities caused by by-product reaction ofsodalite and the productivity.

After the termination of aging, the crystallization is terminated bycooling, diluting or filtering and washing the slurry, or neutralizingthe slurry by adding an acid. In the case of filtering and washing theslurry, it is preferable that washing is carried out until pH of thewashing preferably becomes 12 or less. Also, in the case of neutralizingthe slurry, the acid used for the neutralization is not particularlylimited, and sulfuric acid, hydrochloric acid, nitric acid, carbondioxide gas, oxalic acid, citric acid, tartaric acid, fumaric acid,succinic acid and the like can be used. Sulfuric acid and carbon dioxidegas are preferable, from the viewpoints of preventing corrosion of thedevices and lowering costs. It is preferable that the pH of the slurryis adjusted to 8 to 12. After the termination of the crystallization,the fine zeolite particle of the present invention in the form of slurryis obtained. Further, this slurry may be appropriately subjected tofiltration or centrifugation to separate zeolite precipitates, and theprecipitates are further washed and dried into the form of cake orpowder.

Next, the fine zeolite particle obtained as a primary product may bepulverized as desired, from the viewpoint of adjusting the zeoliteparticle to show a desired average aggregate particle size. Thepulverization may be carried out by directly subjecting the slurry ofthe above-mentioned fine zeolite particle to wet pulverization, oralternatively re-dispersing the resulting fine zeolite particle in asolvent, and thereafter subjecting the dispersion to wet pulverization,or alternatively subjecting a powdery fine zeolite particle to drypulverization. Each of the pulverization methods can be carried out inaccordance with a known method.

For instance, when the fine zeolite particle of the present invention isadded to the detergent composition of the present invention describedbelow, the zeolite particle may be added in a slurry form. In this case,it is preferable to carry out wet pulverization, from the viewpoint ofsimplicity in the preparation steps. The pulverization method employedherein is not particularly limited. For instance, there may be employedpulverizers and the like described in Kagaku Kogakukai Edited, KagakuKogaku Binran (published by Maruzen Publishing, 1988), Fifth Edition,pages 826 to 838. Also, the dispersion medium to be used for wetpulverization includes water, alcohol solvents such as ethanol,surfactants such as polyoxyethylene alkyl ethers, polymer dispersants,and the like. They can be used alone or as a mixed solution of two ormore kinds. When the slurry is subjected to wet pulverization, thezeolite concentration in the slurry is preferably 5% by weight or more,more preferably 10% by weight or more, still more preferably 15% byweight or more, from the viewpoint of productivity. In addition, thezeolite concentration in the slurry is preferably 60% by weight or less,more preferably 55% by weight or less, still more preferably 50% byweight or less, from the viewpoint of the handleability of the zeoliteslurry during the wet pulverization and from the viewpoint of preventionof the re-aggregation of the fine zeolite particle after pulverization.

The fine zeolite particle of the present invention is suitably used for,for instance, detergent builders, water treatment agents, fillers forpaper, resin fillers, oxygen-nitrogen separating agents, adsorbents,catalyst carriers, soil improvers for gardening, polishing agents, andthe like, and especially preferably used as detergent builders.

Further, the detergent composition of the present invention will bedescribed. The detergent composition comprises a surfactant and the finezeolite particle of the present invention. Owing to the high cationicexchange abilities, the low Al ion-eluting property and further the lowturbidity of the zeolite, the detergent composition exhibits excellentdetergency performance and makes rinsing water substantially not turbid,so that the amount of water and the time required for rinsing can beremarkably shortened.

The content of the fine zeolite particle in the detergent composition ofthe present invention is not particularly limited. The content of thefine zeolite particle in the detergent composition is preferably 1% byweight or more, more preferably 3% by weight or more, still morepreferably 5% by weight or more, from the viewpoint of exhibitingsatisfactory detergency performance. In addition, the content of thefine zeolite particle is preferably 60% by weight or less, morepreferably 50% by weight or less, still more preferably 40% by weight orless, from the viewpoint of stability in the production of the detergentcomposition. The content of the fine zeolite particle in the detergentcomposition is preferably from 1 to 60% by weight, more preferably from3 to 50% by weight, still more preferably from 5 to 40% by weight. Inaddition, in the detergent composition of the present invention, theremay be formulated other known zeolites together with the fine zeoliteparticle of the present invention. Such other zeolites may becommercially available zeolites, and the crystal structure of suchzeolites may be P-type, X-type and the like other than the A-type. Also,the zeolites may be a mixture of two or more of these zeolites. Theaverage primary particle size and the average aggregate particle size ofthe other zeolite are not particularly limited. The average primaryparticle size is preferably 10 μm or less, more preferably 5 μm or less,still more preferably 2 μm or less, from the viewpoint of the cationicexchange rate. Also, the average aggregate particle size is preferably15 μm or less, more preferably 10 μm or less, still more preferably 5 μmor less, from the viewpoint of the dispersibility in water. Theproportion of the fine zeolite particle of the present inventioncontained in all the zeolite used is preferably 10% by weight or more,more preferably 20% by weight or more, still more preferably 50% byweight or more, from the viewpoint of securing the exhibition of thedesired effect of the detergent composition of the present invention.

The surfactant to be added to the detergent composition of the presentinvention is not particularly limited. For instance, there can beexemplified nonionic, anionic, cationic and amphoteric surfactants.

Concrete examples of the nonionic surfactants include those knownnonionic surfactants disclosed in “Chapter 3, Section 1 of Shuchi•KanyoGijutsushu (Iryoyo Funmatsusenzai) [Known and Well Used TechnicalTerminologies (Laundry Powder Detergent)]” a publication made by theJapanese Patent Office. Other nonionic surfactants includepolyoxyethylene alkyl phenyl ethers, polyoxyethylene alkylamines,sucrose fatty acid esters, glycerol fatty acid monoesters, higher fattyacid alkanolamides, polyoxyethylene higher fatty acid alkanolamides,amine oxides, alkyl glycosides, alkyl glyceryl ethers, N-alkylgluconamides and the like.

Examples of the anionic surfactants include those known anionicsurfactants disclosed in “Chapter 3, Section 1 of Shuchi•KanyoGijutsushu (Iryoyo Funmatsusenzai) [Known and Well Used TechnicalTerminologies (Laundry Powder Detergent)]” a publication made by theJapanese Patent Office. The counter ions for the anionic surfactant areselected from the group consisting of sodium ion, potassium ion,magnesium ion, calcium ion, a cation formed by protonating an amine suchas ethanolamines, a quaternary ammonium salt, and mixtures thereof.

Examples of the cationic surfactants include those known cationicsurfactants disclosed in “Chapter 3, Section 1 of Shuchi•KanyoGijutsushu (Iryoyo Funmatsusenzai) [Known and Well Used TechnicalTerminologies (Laundry Powder Detergent)]” a publication made by theJapanese Patent Office.

Examples of the amphoteric surfactants include those known amphotericsurfactants disclosed in “Chapter 3, Section 1 of Shuchi•KanyoGijutsushu (Iryoyo Funmatsusenzai) [Known and Well Used TechnicalTerminologies (Laundry Powder Detergent)]” a publication made by theJapanese Patent Office.

The above-mentioned surfactants can be used alone or in admixture of twoor more kinds. In addition, the surfactants can be selected from thoseof the same or different kinds.

The content of the surfactant in the detergent composition of thepresent invention is not particularly limited. The content of thesurfactant in the detergent composition is preferably 1% by weight ormore, more preferably 5% by weight or more, still more preferably 10% byweight or more, from the viewpoint of detergency. Also, the content ofthe surfactant is preferably 90% by weight or less, more preferably 70%by weight or less, still more preferably 60% by weight or less, from theviewpoint of the productivity of the detergent composition. The contentof the surfactant in the detergent composition of the present inventionis preferably from 1 to 90% by weight, more preferably from 5 to 70% byweight, still more preferably from 10 to 60% by weight.

In the detergent composition of the present invention, besides theabove-mentioned surfactant and the fine zeolite particle of the presentinvention, there can be properly added various additives which areusually added to laundry detergents. The content of these additives canbe properly adjusted as long as they do not inhibit the desired effectsof the detergent composition of the present invention.

The above-mentioned additives include, for instance, other inorganicbuilders, organic builders, enzymes, re-deposition preventives,fluorescers, viscosity-controlling agents, solvents, bleaching agents,dispersing agents, perfume, and the like. The inorganic builder besidesthe zeolite includes silicates, carbonates, sulfates, sulfites,condensed phosphates, sodium chloride, and the like, and these salts arepreferably formed with an alkali metal. The organic builder includesorganic alkalizing agents such as alkanolamines such as triethanolamine,diethanolamine and monoethanolamine; organic cation-exchanging agentssuch as aminopolyacetates such as ethylenediaminetetraacetate,oxycarboxylates such as citric acid, polycarboxylates such aspolyacrylic acids and acrylic acid-maleic acid copolymers, and the like,and these salts are preferably formed with an alkali metal or ammonium.The enzyme includes cellulase, amylase, cannase, lipase, protease, andthe like. The re-deposition agent includes polyethylene glycol,polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, andthe like. The viscosity-controlling agent and the solvent include loweralcohols such as isopropanol, glycols such as ethylene glycol, glycerol,and the like. The bleaching agent includes inorganic peroxide bleachingagents such as sodium percarbonate and sodium perborate, or a mixture ofthese inorganic peroxide bleaching agents with a bleaching activator.Examples of the bleaching activator include an organic compound having areactive acyl group for forming an organic peroxide. Concrete examplesof the bleaching activator include sodium lauroyloxybenzenesulfonate,sodium decanoyloxybenzenesulfonate, lauroyloxybenzoic acid,decanoyloxybenzoic acid and the like. Besides them, bleaching activatingcatalysts such as manganese, cobalt and iron complexes can be added as ableaching activator.

The detergent composition of the present invention can be obtained bymixing and stirring each of the components mentioned above according toa known method, and thereafter optionally subjecting the resultingmixture to such a treatment as granulation. Since the compositioncomprises the fine zeolite particle of the present invention, thecomposition is very excellent in the detergency and the rinsingperformance. The detergency and the rinsing performance can be evaluatedby the methods described in Examples set forth below.

The determination values of the sample properties in Examples andComparative examples were measured according to the method set forthbelow. Here, “%” means “% by weight” unless otherwise noted. In thetable, the units for the cationic exchange abilities are each simplyexpressed as “mg/g.”

(1) Average Primary Particle Size

The primary particle size of zeolite particle for 100 or more particlesis measured by a digitizer (commercially available from GRAPHTECCORPORATION, “DIGITIZER KW3300”), on the basis of the scanning electronphotomicrographs of a sample zeolite taken by a field-emission highresolution scanning electron microscope (FE-SEM, commercially availablefrom Hitachi Ltd., S-4000). The number-average value (average primaryparticle size) and the variation coefficient (%) are calculated on thebasis of the entire resulting determination values as population. Here,the variation coefficient is calculated by the following equation:$\begin{matrix}{Variation} \\{{Coefficient}\quad (\%)}\end{matrix} = {\frac{{Standard}\quad {Deviation}\quad ({µm})}{{Average}\quad {Primary}\quad {Particle}\quad {Size}\quad ({µm})} \times 100}$

(2) Powder X-ray Diffraction

The powder sample is subjected to powder X-ray diffraction at roomtemperature (20° C.) by using a powder X-ray diffractometer,commercially available from Rigaku Denki, “RINT 2500 VPC” (light source:CuKα ray, tube voltage: 40 kV, and tube electric current: 120 mA) underthe conditions of a scanning interval of 0.01° in the range of 2θ=5° to40°, a scanning speed of 10°/minute, a divergence vertical limiting slitof 10 mm, a divergence slit of 1°, a light-intercepting slit of 0.3 mm,and a scattering slit being automatic. With taking background levelpoints at 2θ=20°, 28.5°, 37° and 40°, a background curve is drawn bythird-order polynomial, and a peak area A_(peak), an area formed betweenthe diffraction curve in the range of 2θ=20° to 40° and the backgroundcurve is determined. A_(r), which is a proportion of a peak area(A_(peak)) above the background level in all peak area (A_(all)) in therange of 2θ=20° to 40° is calculated from the peak area and all the peakarea as follows:${A_{r}\quad (\%)} = {\frac{A_{peak}}{A_{all}} \times 100}$

The term “all peak area” refers to an area formed between thediffraction curve in the range of 2θ=20° to 40° and a straight line ofintensity zero. In addition, the crystallinity degradation ratio bypulverization is calculated by the following equation: $\begin{matrix}\begin{matrix}{Crystallinity} \\{Degradation}\end{matrix} \\{{Ratio}\quad (\%)}\end{matrix} = {\frac{1 - \left( {A_{r}\quad {of}\quad {Zeolite}\quad {After}\quad {Pulverization}} \right)}{\left( {A_{r}\quad {of}\quad {Zeolite}\quad {Before}\quad {Pulverization}} \right)} \times 100}$

Further, the powder X-ray diffraction intensity ratio (%) is calculatedas a ratio of a powder X-ray diffraction peak intensity (I₄₁₀) having aface distance d=0.3 nm belonging to a face (I₄₁₀) of A-type zeoliteobtained for the zeolite to be analyzed to I₄₁₀ of a commerciallyavailable A-type zeolite (“TOYOBUILDER,” commercially available fromTOSOH CORPORATION, I₄₁₀=32837 cps) having an average primary particlesize of 1 μm or more.

(3) Average Aggregate Particle Size

The particle size distribution is measured with a slurry prepared bydispersing a sample in water as a dispersion medium under conditions ofa refractive index of 1.2, an ultrasonic intensity of 7, anultrasonication irradiation time of 1 minute, and a flow rate of 4,using a laser diffraction/scattering particle size distribution analyzer(commercially available from HORIBA Ltd., LA-920). The median diameter(calculated on the basis of volume) obtained is considered as an averageaggregate particle size (μm).

(4) Cationic Exchange Capacity

The amount 0.2 g of a water-based liquid of 20% zeolite is added to 100mL of an aqueous calcium chloride (100 ppm calcium concentration,calculated as CaCO₃), and stirred at 20° C. for 1 minute or 10 minutes,and the mixture is filtered with a disposable filter with 0.2 μm poresize. Thereafter, 10 mL of the resulting filtrate is taken and assayedfor a Ca content in the filtrate by using a photometric titrationapparatus, and cationic exchange abilities are determined. Incidentally,the Ca content (calculated as the amount of CaCO₃) ion-exchanged per 1 gof the zeolite in 1 minute is referred to as “cationic exchange rate(CER, expressed as mg CaCO₃/g)”, and the Ca content (calculated as theamount of CaCO₃) ion-exchanged per 1 g of the zeolite in 10 minutes isreferred to as “cationic exchange capacity (CEC, expressed as mgCaCO₃/g).”

(5) Turbidity

The turbidity (%) of a water-based liquid of zeolite (zeoliteconcentration: 0.013%) prepared by stirring the zeolite in water havingwater hardness of 4° at room temperature (20° C.) for 10 minutes isdetermined by using a turbidimeter commercially available from MurakamiColor Research Laboratory, reflectance-transmittance meter HR-100.

(6) Detergency

Forty grams of a crystalline silicate (KWS-2, particle size: 11 μm,commercially available from Kao Corporation) is added to a mixedsolution of 24.8 g of a nonionic surfactant (EMULGEN 108, commerciallyavailable from Kao Corporation), 14.8 g of a polyoxyethylene phenylether (commercially available from Nippon Nyukazai) and 0.4 g of apolymer-type dispersant (AQUALOCK FC 600S, commercially available fromNIPPON SHOKUBAI CO., LTD.), and the resulting mixture is homogeneouslymixed with stirring. The resulting silicate-containing liquid mixture isplaced in a 1-L batch-type sand-mill (commercially available from IMEX)together with 500 g of zirconia beads (diameter: 1 mm), and subjected topulverization at a disc rotational speed of 1500 rpm for 60 minutes.Next, 0.3333 g of a liquid mixture containing the silicate after thepulverization (particle size: 2.3 μm) and 0.3333 g of a water-basedliquid of zeolite (zeolite concentration: 20%) are mixed, to give adetergent composition. Five pieces of artificially soiled cloths arewashed by washing with the resulting detergent composition for 10minutes, rinsing for 1 minute and drying using a turg-O-meter (120 rpm,commercially available from Ueshima Seisakusho) in 1 L of water havingwater hardness of 4° at a water temperature of 20° C., and the detergingrate (%) is determined. Here, the deterging rate is determined bymeasuring the reflectances at 550 nm of an unsoiled cloth and theartificially soiled cloth before and after washing by an automaticrecording calorimeter (commercially available from ShimadzuCorporation), and calculated by the following equation. $\begin{matrix}{Deterging} \\{{Rate}\quad (\%)}\end{matrix} = {\frac{\begin{matrix}\left\lbrack {{{Reflectance}\quad {After}\quad {Washing}} -} \right. \\\left. {{Reflectance}\quad {Before}\quad {Washing}} \right\rbrack\end{matrix}}{\begin{matrix}\left\lbrack {{{Reflectance}\quad {of}\quad {Unsoiled}\quad {Cloth}} -} \right. \\\left. {{Reflectance}\quad {Before}\quad {Washing}} \right\rbrack\end{matrix}} \times 100}$

The deterging rate is obtained as an average of 5 pieces of cloths.

The artificially soiled cloths described above are prepared by smearinga cloth (#2003 calico, commercially available from Tanigashira Shoten)with an artificial soil solution having the following composition. Thesmearing of the cloths with the artificial soil solution is carried outusing a gravure roll coater (cell capacity: 58 cm, coating speed: 1m/minute, drying temperature: 100° C., and drying time: 1 minute) madein accordance with Japanese Patent Laid-Open No. Hei 7-270395.

(Composition of Artificial Soil Solution)

The composition of the artificial soil solution is as follows: Lauricacid: 0.44%, myristic acid: 3.09%, pentadecanoic acid: 2.31%, palmiticacid: 6.18%, heptadecanoic acid: 0.44%, stearic acid: 1.57%, oleic acid:7.75%, triolein: 13.06 /o, n-hexadecyl palmitate: 2.18%, squalene:6.53%, liquid crystalline product of lecithin, from egg yolk(commercially available from Wako Pure Chemical Industries): 1.94%,Kanuma red clay for gardening: 8.11%, carbon black (commerciallyavailable from Asahi Carbon.): 0.01%, and tap water: balance.

(7) Rinsing Performance

Using a detergent composition prepared by mixing a zeolite 22%, acrystalline silicate (SKS-6, particle size: 26 μm, commerciallyavailable from Clariant) 11%, and a nonionic surfactant (EMULGEN 108,commercially available from Kao Corporation) 67%, the clothes are washedfor 10 minutes under the conditions of a liquor ratio of 1/20, aconcentration of the detergent composition of 20 g/30 L, and a watertemperature of 20° C. in tap water having water hardness of 4°, and thenrinsed for 4 minutes at a rinsing flow rate of 15 L/minute, using atwin-tub washing machine commercially available from TOSHIBACORPORATION, “GINGA 3.6”. Thereafter, the transparency of the rinsing isvisually confirmed, and the rinsing performance is evaluated on thebasis of the following evaluation criteria. Specifically, after theclothes in the washtub are moved to the side wall of the washtub afterstopping the washing machine, the rinsing performance is evaluated onthe basis of the 3 grade-evaluation criteria:

◯: the case where the rinsing is transparent, and the pulsator at thebottom of the washtub is clearly seen;

Δ: the case where the rinsing is slightly turbid, but the pulsator canbe seen; and

×: the case where the rinsing is turbid and the contour of the pulsatorcannot be clearly seen.

EXAMPLE 1

(1) Preparation of Zeolite

Two-hundred grams of a nonionic surfactant (compound name:polyoxyethylene lauryl ether, EMULGEN 108, commercially available fromKao Corporation) was added to 400 g of an aqueous sodium aluminatesolution (Na₂O: 21.01%, Al₂O₃: 28.18%) contained in a 2 L-stainlesscontainer, while stirring with Teflon agitation blades each having alength of 11 cm at 400 rpm. The resulting mixture was heated at 50° C.for 20 minutes using a mantle heater. The amount 445 g of No. 3 waterglass (Na₂O: 9.68%, SiO₂: 29.83%, commercially available from OsakaKeiso) was added dropwise to the resulting solution over 5 minutes usinga roller pump. After the termination of the dropwise addition, themixture was further stirred for 10 minutes (400 rpm), and heated to 80°C. over 30 minutes while stirring. Thereafter, the mixture was furtheraged for 60 minutes. The resulting water-based liquid of fine zeoliteparticles was filtered, and washed with water until the filtrate had apH of less than 12. The filtrate was dried at 100° C. for 13 hours, andcrushed for 1 minute with a cooking cutter. The resulting powder wassubjected to powder X-ray diffraction measurement. As a result, it wasconfirmed that A-type zeolite (powder X-ray diffraction intensity ratio:46%) was formed. In addition, the average primary particle size of thezeolite particles was 0.03 μm.

(2) Pulverization of Zeolite

A water-based liquid of zeolite prepared by dispersing 10 g of theresulting powder of fine A-type zeolite particles in 40 g ofion-exchanged water was placed in a sealed container (capacity: 250 mL,made of polystyrene) together with 300 g of zirconia balls having adiameter of 5 mm, and pulverized with a ball-mill (300 rpm) for 24hours. The concentration of Al eluted in the filtrate, obtained byultrafiltering the water-based liquid of zeolite after the pulverization(zeolite concentration: 20%) with Ultrafilter Unit USY-1, molecularweight cut off: 10000, commercially available from ADVANTEC, wasquantified by ICP (Inductively coupled plasma spectrometry) analysis.The concentration of the total Al contained in the zeolite in thewater-based liquid of 20% zeolite was 3% of the liquid, and theconcentration of eluted Al obtained by the ICP analysis was 900 ppm. Theproportion of the amount of the eluted Al in the amount of the total Alwas found to be 3%. Incidentally, the proportion of the amount of elutedAl of the zeolite obtained in the above item (1) without pulverizationwas also determined in the same manner as above.

Also, various properties of the zeolite before and after thepulverization were determined in the manner as described above.Incidentally, the zeolite after the pulverization was evaluated usingthose obtained by drying the filtered precipitates, which were obtainedduring the determination of the amount of the eluted Al, at 100° C. for13 hours. In addition, the cationic exchange abilities, the turbidity,the deterging rate, and the rinsing performance were evaluated using thezeolite after the pulverization.

EXAMPLE 2

(1) Preparation of Zeolite

The amount 137 g of a polyethylene glycol (PEG 600, average molecularweight: 600, commercially available from Wako Pure Chemical Industries)was added to 400 g of an aqueous sodium aluminate solution (Na₂O:21.01%, Al₂O₃: 28.18%) contained in a 2 L-stainless container, whilestirring with Teflon agitation blades each having a length of 11 cm at400 rpm. The resulting mixture was heated at 50° C. for 20 minutes usinga mantle heater. The amount 445 g of No. 3 water glass (Na₂O: 9.68%,SiO₂: 29.83%, commercially available from Osaka Keiso) was addeddropwise to the resulting solution over 5 minutes using a roller pump.After the termination of the dropwise addition, the mixture was furtherstirred for 10 minutes (400 rpm), and heated to 80° C. over 30 minutes,while stirring. Thereafter, the mixture was further aged for 60 minutes.The resulting water-based liquid of fine zeolite particles was filtered,and washed with water until the filtrate had a pH of less than 12. Thefiltrate was dried at 100° C. for 13 hours, and crushed for 1 minutewith a cooking cutter. The resulting powder was subjected to powderX-ray diffraction measurement. As a result, it was confirmed that A-typezeolite (powder X-ray diffraction intensity ratio: 48%) was formed. Inaddition, the average primary particle size of the zeolite particles was0.03 μm.

(2) Pulverization of Zeolite

A water-based liquid of zeolite prepared by dispersing 16 g of theresulting powder of fine A-type zeolite particles in 64 g ofion-exchanged water was placed in a pulverizing vessel made of Teflontogether with 500 g of zirconia beads having a diameter of 0.5 mm, and asand-mill pulverization was carried out at 1500 rpm for 20 minutes. Theconcentration of Al eluted in the filtrate, obtained by ultrafilteringthe water-based liquid of zeolite after the pulverization (zeoliteconcentration: 20%) with Ultrafilter Unit USY-1, molecular weight cutoff: 10000, commercially available from ADVANTEC, was quantified by ICPanalysis. The concentration of the total Al contained in the zeolite inthe water-based liquid of 20% zeolite was 3% of the liquid, and theconcentration of eluted Al obtained by the ICP analysis was 700 ppm. Theproportion of the amount of the eluted Al in the amount of the total Alwas found to be 2.3%. In addition, various properties of the zeolitewere determined in the same manner as in Example 1.

EXAMPLE 3

(1) Preparation of Zeolite

Two-hundred grams of a sodium aluminate powder (Na₂O: 40.1%, Al₂O₃:53.8%, NAP-120, commercially available from Sumitomo Chemical Company,Limited) was added to 147 g of a 40% aqueous acrylate polymer solution(Oligomer D, weight-average molecular weight: 10000, commerciallyavailable from Kao Corporation) contained in a 2 L-stainless container,while stirring with Teflon agitation blades each having a length of 11cm at 400 rpm. The resulting mixture was heated at 50° C. for 20 minutesusing a mantle heater. The amount 428 g of No. 3 water glass (Na₂O:9.68%, SiO₂: 29.83%, commercially available from Osaka Keiso) was addeddropwise to the resulting solution over 5 minutes using a roller pump.After the termination of the dropwise addition, the mixture was furtherstirred for 10 minutes (400 rpm), and heated to 80° C. over 30 minuteswhile stirring. Thereafter, the mixture was further aged for 60 minutes.The resulting water-based liquid of fine zeolite particles was filtered,and washed with water until the filtrate had a pH of less than 12. Thefiltrate was dried at 100° C. for 13 hours, and crushed for 1 minutewith a cooking cutter. The resulting powder was subjected to powderX-ray diffraction measurement. As a result, it was confirmed that A-typezeolite (powder X-ray diffraction intensity ratio: 49%) was formed. Inaddition, the average primary particle size of the zeolite particles was0.03 μm.

(2) Pulverization of Zeolite

A water-based liquid of zeolite prepared by dispersing 10 g of theresulting powder of fine A-type zeolite particles in 40 g ofion-exchanged water was placed in a sealed container (capacity: 250 mL,made of polystyrene) together with 300 g of zirconia balls having adiameter of 5 mm, and a ball-mill pulverization was carried out at 300rpm for 24 hours. The concentration of Al eluted in the filtrateobtained by ultrafiltering the water-based liquid of zeolite after thepulverization (zeolite concentration: 20%) with Ultrafilter Unit USY-1,molecular weight cut off: 10000, commercially available from ADVANTEC,was quantified by ICP analysis. The concentration of the total Alcontained in the zeolite in the water-based liquid of 20% zeolite was 3%of the liquid, and the concentration of eluted Al obtained by the ICPanalysis was 700 ppm. The proportion of the amount of the eluted Al inthe amount of the total Al was found to be 2.3%. In addition, variousproperties of the zeolite were determined in the same manner as inExample 1.

Comparative Example 1

(1) Preparation of Zeolite

The amount 211 g of an aqueous sodium hydroxide (48% aqueous NaOH) wasadded to 400 g of an aqueous sodium aluminate solution (Na₂O: 21.01%,Al₂O₃: 28.18%) contained in a 2 L-stainless container, while stirringwith Teflon agitation blades each having a length of 11 cm at 400 rpm.The resulting mixture was heated at 50° C. for 20 minutes using a mantleheater. A mixed solution of 445 g of No. 3 water glass (Na₂O: 9.68%,SiO₂: 29.83%, commercially available from Osaka Keiso) and 236 g of anaqueous calcium chloride (1% aqueous CaCl₂) was added dropwise to theresulting solution over 5 minutes using a roller pump. After thetermination of the dropwise addition, the mixture was further stirredfor 10 minutes (400 rpm), and heated to 80° C. over 30 minutes whilestirring. Thereafter, the mixture was further aged for 5 minutes. Theresulting water-based liquid of zeolite was filtered, and washed withwater until the filtrate had a pH of less than 12. The filtrate wasdried at 100° C. for 13 hours, and crushed for 1 minute with a cookingcutter. The resulting powder was subjected to powder X-ray diffractionmeasurement. As a result, it was confirmed that A-type zeolite (powderX-ray diffraction intensity ratio: 62%) was formed. In addition, theaverage primary particle size of the zeolite particles was 0.2 μm.

(2) Pulverization of Zeolite

The zeolite was pulverized, and the concentration of Al eluted therefromwas quantified by ICP analysis, in the same manner as in Example 1. Theconcentration of the total Al contained in the zeolite in thewater-based liquid of 20% zeolite was 3% of the liquid, and theconcentration of eluted Al obtained by the ICP analysis was 1300 ppm.The proportion of the amount of the eluted Al in the amount of the totalAl was found to be 4.3%. In addition, various properties of the zeolitewere determined in the same manner as in Example 1.

Comparative Example 2

Various properties of the zeolite were determined in the same manner asin Example 1 using a commercially available A-type zeolite (TOYOBUILDER,commercially available from Tosoh Corporation), except that zeolite wasnot pulverized in this Comparative Example.

Comparative Example 3

Various properties of the zeolite were determined in the same manner asin Example 1 using a commercially available 4A zeolite (TOYOBUILDER,commercially available from Tosoh Corporation). Here, the concentrationof the total Al contained in the zeolite in the water-based liquid of20% zeolite was 3% of the liquid, and the concentration of eluted Alobtained by ICP analysis after the pulverization was 1200 ppm. Theproportion of the amount of the eluted Al in the amount of the total Alwas found to be 4%.

Comparative Example 4

The amount 155 g of propylene glycol (molecular weight: 76, commerciallyavailable from Wako Pure Chemical Industries) was added to 400 g of anaqueous sodium aluminate solution (Na₂O: 21.01%, Al₂O₃: 28.18%)contained in a 2 L-stainless container, while stirring with Teflonagitation blades each having a length of 11 cm at 400 rpm. The resultingmixture was heated at 50° C. for 20 minutes using a mantle heater. Theamount 445 g of No. 3 water glass (Na₂O: 9.68%, SiO₂: 29.83%,commercially available from Osaka Keiso) was added dropwise to theresulting solution over 5 minutes using a roller pump. After thetermination of the dropwise addition, the mixture was further stirredfor 10 minutes (400 rpm), and heated to 80° C. over 30 minutes whilestirring. Thereafter, the mixture was further aged for 60 minutes. Theresulting water-based liquid of fine zeolite particles was filtered, andwashed with water until the filtrate had a pH of less than 12. Thefiltrate was dried at 100° C. for 13 hours, and crushed for 1 minutewith a cooking cutter. The resulting powder was subjected to powderX-ray diffraction measurement. As a result, it was confirmed that A-typezeolite (powder X-ray diffraction intensity ratio: 61%) was formed. Inaddition, the average primary particle size of the zeolite particles was0.2 μm. The zeolite was pulverized, and evaluated in the same manner asin Example 1. The concentration of the total Al in the water-basedliquid of 20% zeolite was 3% of the liquid, and the concentration ofeluted Al obtained by the ICP analysis was 1300 ppm. The proportion ofthe amount of the eluted Al in the amount of the total Al was found tobe 4.3%. In addition, various properties of the zeolite were determinedin the same manner as in Example 1.

The feeding composition of zeolite is shown in Table 1, and the resultsdescribed above are summarized in Table 2.

TABLE 1 Examples Comparative Examples 1 2 3 1 2 3 4 Feeding CompositionMolar Ratio SiO₂/Al₂O₃ 2.0 2.0 2.0 2.0 — — 2.0 Na₂O/Al₂O₃ 1.9 1.9 1.93.0 — — 1.9 CaO/Al₂O₃ 0 0 0 0.02 — — 0 Na₂O/H₂O 0.078 0.078 0.078 0.065— — 0.078 Al₂O₃/H₂O 0.042 0.042 0.042 0.022 — — 0.042 CrystallizationInhibitor 19 14 6.8 0 0 0 15 (%) Solid Content (%) 36 38 41 35 — — 37Product Composition Molar Ratio SiO₂/Al₂O₃ 2.0 2.0 2.0 2.0 2.0 2.0 2.0Na₂O/Al₂O₃ 1.1 1.1 1.0 1.1 1.1 1.1 1.1 CaO/Al₂O₃ 0 0 0 0.02 0 0 0Crystal Form A-Type A-Type A-Type A-Type A-Type A-Type A-Type

TABLE 2 Comparative Examples 3 Examples 2 Commercially 1 2 3 1Commercially Available 4 Prepared and Prepared and Prepared and Preparedand Available Product, Prepared and Zeolite Pulverized PulverizedPulverized Pulverized Product Pulverized Pulverized CrystallizationInhibitor Nonionic Polyethylene Acrylate — — — Propylene (MolecularWeight) Surfactant Glycol Polymer Glycol (454) (600) (10000) (76)Average Primary Particle Size (μm) [Variation Coefficient] (%) BeforePulverization 0.03 0.03 0.03 0.2 1.8 1.8 0.2 [16] [23] [14] [30] [30][30] [30] After Pulverization 0.03 0.03 0.03 0.03 — 0.04 0.03 [20] [25][20] [18] [100] [20] Average Aggregate Particle Size (μm) BeforePulverization 15 17 9.9 3.2 4.0 4.0 16 After Pulverization 0.37 0.330.40 0.38 — 0.48 0.40 A_(r) (%) Before Pulverization 53.4 52.7 50.4 61.066.2 66.2 60.6 After Pulverization 35.1 42.3 34.0 27.2 — 43.3 27.4Crystallinity Degradation Ratio (%) 34.3 19.7 32.5 55.4 — 34.6 54.8Amount of Eluted Al (%) Before Pulverization 0.7 0.2 0.3 0.2 0.1 0.1 0.2After Pulverization 3.0 2.3 2.3 4.3 — 4.0 4.3 Powder X-Ray DiffractionIntensity Ratio (%) Before Pulverization 46 48 49 62 100 100 61 AfterPulverization 28 28 30 24 — 47 25 Cationic Exchange Rate (mg/g) 220 220220 210 160 210 210 Cationic Exchange Capacity (mg/g) 220 220 220 220220 220 220 Turbidity (%) 17 25 29 24 50 32 30 Detergent CompositionDeterging Rate (%) 60 60 60 45 50 47 45 Rinsing Performance ◯ ◯ ◯ ◯ X ΔΔ

It is clear from Examples 1 to 3 that there can be obtained fine A-typezeolite particles having an average primary particle size of 0.1 μm orless by carrying out the reaction of preparing zeolite in the presenceof crystallization inhibitor according to the process for preparing finezeolite particles of the present invention. In Comparative Example 4where the reaction of preparing zeolite is carried out in the presenceof a propylene glycol, which is an organic compound having anoxygen-containing functional group, the molecular weight of the compoundis 76, so that fume zeolite particles having an average primary particlesize of 0.1 μm or less are not obtained.

In addition, the average aggregate particle size of the zeoliteparticles of Examples and Comparative Examples can be adjusted to 0.4 μmor less by an appropriate pulverization. However, in the zeoliteparticles of Comparative Examples 1, 3 and 4, of which average primaryparticle size before pulverization is more than 0.1 μm after thepulverization, the crystallinity degradation progresses, thedeterioration of the average primary particle size distribution isobserved, and the amount of the eluted Al is increased. Therefore, it isseen that the deterging rate and/or the rinsing performance of thedetergent compositions obtained using the zeolite is lowered. On theother hand, in Examples 1 to 3, the progress of the crystallinitydegradation (for example, crystallinity degradation ratio) issuppressed, and the average primary particle size distribution is notsubstantially changed, even when the zeolite is pulverized. Therefore,in these Examples, there are obtained fine zeolite particles which havea desired average aggregate particle size and excellent cationicexchange abilities, so that it is seen that the deterging rate and therinsing performance of the detergent compositions obtained by using thezeolite are high.

Industrial Applicability

According to the present invention, there can be obtained fine zeoliteparticles having an average primary particle size of 0.1 μm or less andexcellent cationic exchange abilities, with a small amount of Al elutedin water in a water-based liquid as well as a low turbidity of water ofthe liquid. In addition, there can be obtained a detergent compositioncomprising the fine zeolite particles, which is highly excellent in thedetergency and rinsing performance. The fine zeolite particle of thepresent invention is suitably used for detergent builders, watertreatment agents, fillers for paper, resin fillers, oxygen-nitrogenseparating agents, adsorbents, catalyst carriers, soil improvers forgardening, polishing agents, and the like.

What is claimed is:
 1. A fine A-type zeolite particle having an averageprimary particle size of 0.1 μm or less and a variation coefficient of90% or less, wherein a ratio of a peak area above a background level toall peak area in the range of 2θ=20° to 40° in a powder X-raydiffraction spectrum of said fine A-type zeolite particle is 30% ormore.
 2. The fine A-type zeolite particle according to claim 1, whereinthe fine A-type zeolite particle has an average aggregate particle sizeof 0.4 μm or less.
 3. The fine A-type zeolite particle according toclaim 1 or 2, wherein when water-based liquid of the particle isprepared, a ratio of the amount of Al eluted in water is less than 4% byweight of all the amount of Al contained in the zeolite.
 4. The fineA-type zeolite particle according to claim 1, wherein the fine A-typezeolite particle has a cationic exchange rate is 180 mg CaCO₃/g or more.5. A process for preparing the fine A-type zeolite particle of claim 1,comprising reacting a silica source with an aluminum source in thepresence of an organic compound having an oxygen-containing functionalgroup and a molecular weight of 100 or more.
 6. The process according toclaim 5, wherein the oxygen-containing functional group is at least oneof OR group and COOR group, wherein R is at least one member selectedfrom a saturated or unsaturated organic group having 1 to 22 carbonatoms, hydrogen atom and an alkali metal atom.
 7. A detergentcomposition comprising a surfactant and the fine A-type zeolite particleof claim 1.